CN1134989A - Method of recovering antimony and bismuth from copper electrolyte - Google Patents

Abstract

A method of recovering antimony and bismuth from copper electrolyte comprises the steps of immersing a pure copper material in the copper electrolyte, so that the iron ions are reduced from Fe3+ ions to Fe2+ ions, using a mixture of dilute sulfuric acid and sodium chloride adjusting the acidity or acidic concentration, to selectively elute the bismuth and antimony wherein if the final concentration of bismuth is adjusted to be 0.02 g/l or less in the bismuth election, it is possible to keep the maximum concentration of bismuth in the antimony eluate in the elution of antimony after selective bismuth elution to 0.01 g/l or less.

Description

From copper electrolyte, reclaim the method for antimony and bismuth

The present invention relates to optionally reclaim the improvement of the method for the impurity antimony that comprised in the employed copper electrolyte of copper electrolyte refining and bismuth.

In traditional copper electrolyte refining, copper removal also contains several metals like gold, silver, nickel, arsenic, antimony, bismuth etc. outward in the anode, and wherein some is gone out from the anode wash-out together with copper.For example, antimony and bismuth are come out from the anode wash-out with copper, and when they accumulate in electrolytic solution when surpassing finite concentration, and therefore they and copper coprecipitation reduced the quality of electrolytic copper.So,, be necessary refining electrolytic solution for the concentration that makes these impurity remains below on certain level.

The main method that is used for refining solution is that electrolytic copper is removed method.But this method efficiency is low, and with regard to Working environment it neither be gratifying.

In recent years, proposed following method and be used for eliminating these shortcomings: used S-WAT at electrolytic solution, and by copper electrolyte is contacted with the chelating resin that is used for optionally absorbing the chelating resin of antimony (Sb), bismuth (Bi) and iron (Fe) or is used for optionally absorbing antimony (Sb), and subsequently by elutriant is contacted with chelating resin, antimony and bismuth are separated from copper electrolyte and reclaimed (Japanese Patent discloses KOKAIno.Showa 60-50192 and KOKAI no.Heisei 2-141541 first, etc.).

Yet above-mentioned control method uses hydrochloric acid as elutriant (eluant), therefore with regard to cost and the electrolytic copper removal method of making peace does not have difference.In addition, for example since the sneaking into of air be difficult to regulate current potential and be maintained to the ideal value.

Below be about some descriptions of copper electrolyte purified.

Isolate the method for antimony and bismuth

Usually, because antimony has similar chemical property with bismuth, so they are difficult for isolating.

Traditionally, recommendation is used for from what copper electrolyte was removed antimony and bismuth: electrolytic copper is removed method, wherein uses by certain material, and for example plumbous insoluble anode that makes is finished the electrolysis of copper electrolyte, after copper is removed, take out the anode sludge (Slime) that contains antimony and bismuth like this; The neutral method wherein adds for example material of sodium bicarbonate in copper electrolyte; The sedimentary method of sulfhydrate has wherein blasted hydrogen sulfide in copper electrolyte, antimony and bismuth just are removed with the sulfhydrate precipitation like this; And the TANPAN production method, wherein concentrate copper electrolyte to form copper sulfate crystal, so antimony and bismuth obtain removing with common sedimentary impurity.

But, in these methods, compare much more copper with the impurity that hope is removed and be removed, so efficient is low.

Recently, a kind of copper electrolyte method of refining of resin that uses is put in the practical application.

From chelating resin optionally when wash-out antimony and bismuth, wash-out bismuth at first, however thoroughly do not separate, so just exist a small amount of antimony to be mingled in problem in the bismuth that wash-out goes out.

If wash-out is insufficient, residue in bismuth on the chelating resin in antimony wash-out subsequently by wash-out, and when the solution that goes out from wash-out during electrolytic extraction antimony, the purity drop of gained antimony.In other words, because the precipitation potential difference of antimony and bismuth is very little, when removing them by electrolytic extraction, antimony has caused the bismuth purity drop that reclaims, and vice versa.Elutriant (Eluant)

Usually use hydrochloric acid to come the antimony and the bismuth of wash-out by the chelating resin absorption as elute soln.

When using hydrochloric acid to carry out wash-out, antimony and bismuth are removed together and they can not be separated at synchronization.Therefore, in the process that antimony and bismuth are reclaimed from wash solution, it is difficult reclaiming antimony and bismuth respectively.

In addition, when the mixture that uses dilute sulphuric acid and sodium-chlor carries out wash-out, antimony and the bismuth concentration ratio in elutant, Bi/Sb only is 1.3 usually, and small like this difference makes and is difficult to obtain selectivity.

Fe ³⁺Influence

Copper electrolyte is contacted with chelating resin and absorbing antimony and bismuth, and carrying out in this process of wash-out with dilute hydrochloric acid subsequently, if Fe is arranged in the copper electrolyte ³⁺, its type resin that can be chelated absorbs, and since its can not be gone out by the dilute hydrochloric acid wash-out, so it accumulate and has reduced the ability of this resin absorption antimony and bismuth in chelating resin.

In order to prevent to absorb Fe ³⁺, a kind of method that promptly flows through in copper electrolyte wink on the resin that still is in the electrolytic reducing environment that makes is arranged, but it lacks handiness.

In addition, have a kind ofly when wash-out antimony and bismuth from chelating resin, adopt high density (6N or higher) hydrochloric acid to come wash-out to go out to be absorbed in Fe in the chelating resin ³⁺Method, but because hydrochloric acid expensive, this method is also uneconomical.

The generation of chlorine in the electrolytic extraction

Using electrolytic extraction from wash solution (eluate solution), to reclaim in the process of antimony and bismuth, when in muriatic groove, carrying out electrolysis, understanding usually, and must handle it for safety at anode side generation chlorine.

The reusability of elutant (Eluate).

Usually, when making spent ion exchange resin remove impurity, when the wash-out of absorbate, produced a large amount of solution, therefore needed main equipment or device to be used for handling or storing these solution, thereby increased initial investment.

Often use the dilute hydrochloric acid and the mixture of sodium-chlor or the mixture of sulfuric acid and sodium-chlor to carry out wash-out, will adopt neutralization when not excessive recovery is contained in antimony in the elutant and bismuth, therefore be difficult to reuse this elutant.

Therefore, wish to set up a kind of method so that using chelating resin to absorb and removing antimony and the bismuth that is dissolved in the copper electrolyte, and the mixture that uses sulfuric acid and sodium-chlor optionally wash-out go out after antimony and the bismuth, use electrolytic extraction to reclaim metallic antimony and bismuth.

Wish to find a kind of method, in order to improve the efficient that reclaims metallic antimony and bismuth by in the wash-out that carries out chelating resin, reusing elutant, and further seek a sharp method, be used for after the elutant electrolytic extraction antimony and bismuth of the antimony that goes out by chelating resin institute wash-out and bismuth, by the investment of carrying out continuously reducing equipment from the wash-out and the electrolytic extraction metal of chelating resin.

One of purpose of the present invention provides a kind of method, and it will eliminate the problems referred to above also can regulate the redox-potential of copper electrolyte to simplify the concentration control of contained iron ion in the copper electrolyte as far as possible in the method for above-mentioned recovery Sb and Bi.

Another object of the present invention is to state a certain characteristic aspect of purpose in realization a kind of method that comprises following steps is provided: reduce Fe by immerse copper product in the copper electrolyte that contains impurity Sb, Bi and Fe ³⁺, and regulate the redox-potential to 650 millivolt of copper electrolyte or lower; Copper electrolyte is contacted with chelating resin to absorb Sb and Bi; Elute soln is contacted with chelating resin to reclaim Sb and Bi.

In the method that is used for reclaiming respectively antimony and bismuth of the present invention, by change vitriolic concentration optionally wash-out go out to be chelated the antimony of type resin absorption and bismuth to obtain antimony elutant and bismuth elutant, and it is 1 that the bismuth elutant preferably is neutralized to the pH value, and in removing the bismuth elutant behind contained a small amount of antimony, this bismuth elutant of electrolytic extraction is then carried out electrolytic extraction for the antimony elutant after finishing neutralization or hydrolysis.

In the method for the invention, with copper electrolyte be filled in before a chelating resin in the pillar contacts, make it by a pillar that is filled with copper sheet, the Fe in the copper electrolyte like this ³⁺Be reduced into Fe ²⁺Absorbed by resin preventing, and then copper electrolyte is contacted with chelating resin.After antimony and bismuth are absorbed, by pushing up flushing pillar extremely down, use the mixture of sulfuric acid and sodium-chlor to flow through pillar to carry out wash-out then as elutriant and by the end to top with hot water.At this moment, change vitriolic concentration, use electrolytic extraction from wash solution separately, to reclaim metallic antimony and bismuth then optionally to reclaim antimony and bismuth.

In the selective elution of bismuth, be lower than 0.02 grams per liter by the ultimate density that makes bismuth, and in the wash-out of antimony, be lower than 0.01 grams per liter by the concentration that makes bismuth, might reclaim highly purified metallic antimony by wash solution is carried out electrolytic extraction.

According to another feature, another object of the present invention provides the method that is used for optionally reclaiming from copper electrolyte antimony and bismuth, and this method comprises following steps; (1) copper electrolyte is contacted will be present in the Fe in the cupric electrolysis with metallic copper ³⁺Iron ion is reduced into Fe ²⁺The iron reduction process of iron ion.(2) reducing solution that obtains is contacted with chelating resin, thereby with the absorption process of antimony in the chelating resin Electolyte-absorptive and bismuth.(3) flushing process of usefulness hot water injection chelating resin.(4) bismuth elution process, wherein 40 to 60 degrees centigrade, the bismuth elutriant that contains the sulfuric acid of 20 to 30 grams per liters and the sodium-chlor of 120 to 180 grams per liters contact with the chelating resin that washed with wash-out to go out bismuth and obtain the wash solution of bismuth.(5) antimony elution process wherein contacts 40 to 60 degrees centigrade, the antimony elutriant that contains 100 to the 250 grams per liter sulfuric acid and the sodium-chlor of 120 to 180 grams per liters with wash-out to go out antimony and obtain the wash solution of antimony after wash-out goes out bismuth with chelating resin.

Fig. 1 is the schema of expression technology of the present invention.

Fig. 2 is the figure (elution curve) that describes to flow through liquor capacity (BV) and eluate grade relation, uses sodium-chlor and the antimony of sulfuric acid mixture and the wash-out state of bismuth with expression.

Fig. 3 is that the figure (elution curve) that describes to flow through liquor capacity (BV) and eluate grade relation has used the antimony of thiocarbamide and sulfuric acid mixture and the wash-out state of bismuth in order to expression.

Fig. 4 has represented to immerse in electrolytic solution and do not immerse under the situation of copper sheet, concentration of iron is absorbed dose, redox-potential and the concentration of iron of copper electrolyte after chelating resin absorbs of 0.4 grams per liter, 0.8 gram liter, 1.6 grams per liters and 2.4 grams per liters, in order to immerse the result of copper sheet in the expression copper electrolyte.

Fig. 5 is the schema of antimony of the present invention and bismuth removal process.

Fig. 6 is the explanatory view of employed electrolyzer in the embodiment of the invention.

Fig. 7 describes when the mixture of the sodium-chlor of sulfuric acid that uses 30 grams per liters and 180 grams per liters and when making it top down flow through pillar during at 40 and 50 degrees centigrade, the required figure that concerns between liquor capacity (BV) and the bismuth eluate grade that flows through.

Fig. 8 describes when the mixture of the sodium-chlor of sulfuric acid that uses 30 grams per liters and 180 grams per liters and when making it flow through pillar from bottom to up during at 50 and 60 degrees centigrade, the required figure that concerns between liquor capacity (BV) and the bismuth eluate grade that flows through.

Fig. 9 is that the mixture of describing the sodium-chlor of sulfuric acid by making 30 grams per liters respectively 50 and 60 degrees centigrade time the and 180 grams per liters supremely flows through pillar and after the wash-out bismuth end of by, the required figure that concerns between liquor capacity (BV) and the antimony eluate grade that flows through when using the mixture of the sodium-chlor of the sulfuric acid of 250 grams per liters and 150 grams per liters to flow through pillar from bottom to up in the time of 50 and 60 degrees centigrade.

Figure 10 is antimony and the concentration of bismuth and the figure of flowing time relation in the expression wash solution.

The technical process of one embodiment of the present of invention is illustrated among Fig. 1.

Among this embodiment, at first, the redox-potential (ORP) that contains the copper electrolyte of impurity Sb, Bi and Fe when adjustment to be making it to be lower than 650 millivolts (for saturated calomel electrode (SCE) time), and to adjust redox-potential be important by immerse copper product in copper electrolyte.By such way, the Fe in being stored in copper electrolyte ³⁺Ion has been reduced into Fe ²⁺Ion.To dissolve in the copper of copper electrolyte be principal element in the copper electrolyte but not impurity by carrying out such reduction.In addition, such copper is controlled without any influence for the concentration that is contained in the foreign ion in the copper electrolyte.It seems preferably fine copper of copper product from these aspects.

The shape that immerses the copper product of copper electrolyte can be bulk, sheet, particulate state etc.

Next step, the copper electrolyte that makes electromotive force carry out adjusting as mentioned above contacts with chelating resin so that chelating resin absorbs antimony and bismuth.Because most of iron has been reduced into Fe ²⁺Ion, the amount of absorbed iron is very little.

About chelating resin, can use the Epolas MX-2 of known Miyoshi oil company manufacturing, the Duo-lite C-467 of Sumitomo chemical company manufacturing and the Uniseleck UR-3300 that Unitika makes etc.

Go out the elutriant of antimony and bismuth about wash-out from the above-mentioned chelating resin that has absorbed antimony and bismuth, can use and contain sodium-chlor and vitriolic solution, or contain thiocarbamide and vitriolic solution.These elutriant prices are not high and be easy to recycling, therefore might reduce the cost of refining process.

In containing the above-mentioned solution of sodium-chlor and vitriolic, wish sodium chloride concentration between 60 and 180 grams per liters, as then better between 120 to 180 grams per liters.In addition, wish sulfuric acid concentration between 30 and 200 grams per liters, as then better between 50 and 200 grams per liters.

In addition, contain in thiocarbamide and the vitriolic situation, wish thiourea concentration between 5 and 20 grams per liters, as then better between 10 and 20 gram liters at above-mentioned solution.In addition, wish sulfuric acid concentration between 25 and 300 grams per liters, as then better between 150 and 200 grams per liters.

If the elutriant temperature is low excessively when above-mentioned elutriant is contacted with chelating resin, the elution of reactive of Sb and Bi is also with slack-off.In addition, if temperature is too high, and if elutriant be to contain sodium-chlor and vitriolic solution, the speed of Sb and Bi elution of reactive can not improve, especially temperature is higher than under 40 degrees centigrade the condition; If elutriant is for containing thiocarbamide and vitriolic solution, the decomposition of thiocarbamide can aggravate, especially under temperature is higher than 50 degrees centigrade condition.If elutriant is to contain sodium-chlor and vitriolic solution, the temperature of wishing elutriant is between 10 and 60 degrees centigrade, as then better between 30 and 40 degrees centigrade.In addition, if elutriant is wished the elutriant temperature between 25 and 60 degrees centigrade for containing thiocarbamide and vitriolic solution, as then better between 30 and 50 degrees centigrade.

Embodiment 1 to 4, comparing embodiment 1 to 4

The functional group of the Epolas chelating resin that the Miyoshi oil company makes is a Hydrogen.

Next, with in the ferric sulfate vitriolization of 200 grams per liters in order to the preparation Fe ³⁺Concentration is respectively four kinds of solution of 0.4 grams per liter, 0.8 grams per liter, 1.6 grams per liters and 2.4 grams per liters, and each solution is equally divided into two parts.Divide equally one of solution and use (comparing embodiment 1,2,3 and 4) same as before, and in each divides equally second half of solution, immerse copper sheet to reduce redox-potential ( embodiment 1,2,3 and 4).The electromotive force of the solution of Shi Yonging is 650 millivolts same as before, and the electromotive force that has wherein immersed the solution of copper sheet is approximately 580 millivolts.

In good for both sides type solution, immerse above-mentioned chelating resin and descend stirring 60 minutes at 40 degrees centigrade.

Next, separate chelating resin and solution, and survey the amount of the iron of the type resin absorption that is chelated in each case, gained the results are shown in the table 1.

The iron that the total iron of table 1 absorbs

(grams per liter) (grams per liter resin) embodiment 1 0.4 2.0 embodiment 2 0.8 2.7 embodiment 3 1.6 4.2 embodiment 4 2.4 6.2 comparing embodiments 1 0.4 6.5 comparing embodiments 2 0.8 10.9 comparing embodiments 3 1.6 16.6 comparing embodiments 4 2.4 18.3

By in copper electrolyte, immersing copper sheet, can reduce the redox-potential of copper electrolyte effectively as can be seen from Table 1, and just can suppress the absorption of iron like this.

Embodiment 5

The functional group of the Epolas MX-2 chelating resin that the Miyoshi oil company makes is a Hydrogen.

Next, stirred 60 minutes down at 400 milliliters of copper electrolytes (antimony 0.55 grams per liter, bismuth 0.52 grams per liter), 20 milliliters of such resins of middle immersion and at 60 degrees centigrade.

Behind this resin of distilled water flushing, it is immersed in the vitriolic solution of 200 milliliters of sodium-chlor that contain 120 grams per liters and 100 grams per liters and 10 degrees centigrade down stirring 60 minutes go out antimony and bismuth with wash-out.The rate of recovery that the result demonstrates antimony and bismuth is 52.3% (by weight).

Embodiment 6 to 9

Except eluting temperature is respectively 25,40,50 and 60 degrees centigrade, these embodiment are undertaken by the mode identical with embodiment 5.The results are shown in the table 2.

Table 2

The rate of recovery of elutriant temperature antimony+bismuth

(degree centigrade) (% weight) embodiment 5 10 52.3 embodiment 6 25 54.5 embodiment 7 40 69.8 embodiment 8 50 71.9 embodiment 9 60 73.4 embodiment 10 to 15

Except sodium-chlor and vitriolic concentration were as shown in table 3, these embodiment were undertaken by the mode identical with embodiment 6 under 25 degree of taking the photograph.The results are shown in the table 3.

Table 3

The rate of recovery of the concentration antimony+bismuth in the elutriant

(grams per liter) (% weight)

Sodium-chlor sulfuric acid embodiment 10 60 100 12.2 embodiment 11 120 30 43.2 embodiment 12 120 50 53.7 embodiment 6 120 100 54.5 embodiment 13 120 120 55.2 embodiment 14 120 200 80.8 embodiment 15 180 100 79.0

In embodiment 14 and 15, the concentration of sodium-chlor is on the saturated level.

Preferably use as can be seen from table 2 and table 3 and to contain sodium-chlor and vitriolic solution elutriant as wash-out antimony and bismuth.

Embodiment 16 to 19

As doing among the embodiment 5, be used to absorb the chelating resin of Sb and Bi with distilled water flushing after, it is immersed in the vitriolic solution of 200 milliliters of thiocarbamides that contain 20 grams per liters and 200 grams per liters, and stirred 60 minutes under temperature as shown in table 4, then Sb and Bi are come out by wash-out.The rate of recovery of Sb and Bi is shown in Table 4.

Table 4

The rate of recovery of elutriant temperature antimony+bismuth

(degree centigrade) (% weight) embodiment 16 25 31.5 embodiment 17 40 42.1 embodiment 18 50 42.1 embodiment 19 60 37.9

The rate of recovery of antimony+bismuth slightly descends in embodiment 19.This may be because the part thiocarbamide has decomposed.

Embodiment 20 to 28

Except thiocarbamide and vitriolic concentration were as shown in table 5, these embodiment were according to carrying out with embodiment 17 identical modes.Gained the results are shown in the table 5.

Table 5

The rate of recovery of concentration antimony+bismuth in the elutriant

(grams per liter) (% weight)

Sulphur gland sulfuric acid embodiment 20 5 200 11.4 embodiment 21 10 25 2.1 embodiment 22 10 50 5.8 embodiment 23 10 100 13.4 embodiment 24 10 150 21.5 embodiment 25 10 200 30.2 embodiment 26 10 300 20.6 embodiment 27 15 200 36.5 embodiment 17 20 200 42.1 embodiment 28 20 300 42.6

Preferably use as can be seen by table 4 and table 5 and to contain thiocarbamide and vitriolic solution elutriant as wash-out antimony and bismuth.

Embodiment 29

The Duo-lite C-467 chelating resin that 100 milliliters of Sumitono chemical companies are made is packed in the post, and the functional group of this chelating resin is a Hydrogen.

Next, the copper sheets that weight are about 50 grams immerse in the copper electrolytes with Fe ³⁺Ion is reduced to Fe ²⁺Ion, and make wherein that antimony concentration is that 0.55 grams per liter, bi concns are 0.52 grams per liter and Fe ²⁺Ionic concn is that the electrolytic solution (redox potential is 580 millivolts) of 0.4 grams per liter flows through above-mentioned pillar.Required flow condition is: the required flow volume of 60 degrees centigrade required yield temperature, the required flow rate of SV10 (10 liters of/hour per 1 liter of resins) and BV100.

In addition, the distilled water with required flow volume of BV20 is also taken away copper electrolyte by pillar to wash above-mentioned chelating resin fully when 60 spend.

Then, make the thiocarbamide that contains 10 grams per liters and the vitriolic solution of 200 grams per liters pass through pillar.Required flow condition is: the required flow volume of 40 degrees centigrade required yield temperature, the required flow rate of SV3 and BV15.The result represents that the rate of recovery of antimony+bismuth is 19.8% (by weight).

Embodiment 30

The functional group that the Epolas MX-2 chelating resin that 100 milliliters of Miyoshi oil companies are made is packed into a pillar and this chelating resin is a Hydrogen.

Next, in copper electrolyte, immerse copper sheets that weight is about 50 grams with Fe ³⁺Ion is reduced to Fe ²⁺Ion, and make wherein that antimony concentration is that 0.55 grams per liter, bi concns are 0.52 grams per liter and Fe ²⁺Ionic concn is that the copper electrolyte (redox potential is 580 millivolts) of 0.4 grams per liter passes through above-mentioned pillar.Required flow condition is: the required flow rate of 60 degrees centigrade required yield temperature, SV10 (10 liters of/hour per 1 liter of resins) and the required flow volume of BV100 (100 liters of per 1 liter of resins).

In addition, making required flow volume is that the distilled water of 20BV flows through pillar to wash above-mentioned chelating resin and to take away copper electrolyte fully under 60 degrees centigrade.

Then, contain the sodium-chlor of 180 grams per liters and the vitriolic solution stream of 100 grams per liters and cross pillar.Required flow condition is: the required flow volume of 40 degrees centigrade required yield temperature, the required flow rate of SV3 and BV15.The result represents that the clearance of antimony+bismuth is 91.6% (by weight).

Fig. 2 has represented the antimony that goes out for the required flow volume institute wash-out that is up to BV15 and the concentration of bismuth.

Embodiment 31

The Epolas MX-2 chelating resin that 100ml Miyoshi oil company is made fills in the post, and functional group is a Hydrogen.To synthesize Fe to form in the ferric sulfate vitriolization of 200 grams per liters ³⁺Solion, and immerse this solution so that Fe at copper sheet with about 50 grammes per square metres ³⁺Ion is reduced into Fe ²⁺Behind the ion, make it pass through pillar, thereby absorb antimony and bismuth with chelating resin.

Next, in order to take away all copper electrolytes fully, in the time of 60 degrees centigrade, reach BV20 (20 liters/rise resin) until flowing with distilled water washing resin, the vitriolic mixture that makes the thiocarbamide of 10 grams per liters and 200 grams per liters then in the time of 40 degrees centigrade is by pillar, and wherein required flow rate is SV3 (3 liters/hour/rise resin).

Required flow volume is BV20 (20 liters/rise resin), and has measured the rate of recovery of antimony and bismuth.The results are shown among Fig. 3.In other words, Fig. 3 has represented 40 degrees centigrade of following concentration of antimony and bismuth in the wash solution of vitriolic mixture till its required flow volume arrival BV20 of thiocarbamide and 200 grams per liters of 10 grams per liters.As can be seen from Figure 3, antimony and bismuth are come out by wash-out.

Embodiment 32 to 35, comparing embodiment 5 to 8

The functional group of the UR-3300 chelating resin that Unitika company limited makes is a Hydrogen.

Ferric sulfate solution is synthesized Fe to form in the sulphuric acid soln of 200 grams per liters ³⁺Solion, and it is divided into two parts.Put into copper sheet in one of resulting solution, another part uses same as before.Chelating resin is put into resulting solution 40 degrees centigrade the time and stirred 60 minutes.Form four types resulting solution, wherein iron concentration is 0.4 grams per liter (embodiment 32, comparing embodiment 5), 0.8 grams per liter (embodiment 33, comparing embodiment 6), (embodiment 34 for 1.6 grams per liters, comparing embodiment 7) and 2.4 grams per liters (embodiment 35, comparing embodiment 8).

When Fig. 4 has represented to add in the solution (embodiment) and has not added (comparing embodiment) copper sheet, the absorbed dose (grams per liter resin) of the UR-3300 after absorbing, redox-potential (ORP) value and iron concentration.As can be seen from Figure 4, by using copper sheet, can suppress chelating resin and absorb iron ion.

In other words, when adding copper sheet in the solution, absorb the concentration of back iron ion in solution and compare with starting point concentration and only reduced by 0.3 grams per liter or still less (with Fe ²⁺Exist), the absorbed dose of ferric ion in chelating resin just only is 6 grams per liter resins or still less like this, and when not adding copper sheet in solution, the amount that absorbs the iron ion of back Chinese blister beetle mould assembly resin absorption has increased, so the concentration of iron ion has reduced greatly.

In addition, if do not add copper sheet in the solution, even can find out that at iron concentration redox-potential (ORP) still is higher than 650 millivolts near zero the time from absorbing the result.It is noted that the metal that is reclaimed is actually antimony and bismuth, and does not almost have iron when the absorption of putting into and stirring iron ion wherein in elutriant repressed chelating resin.

In the method that reclaims antimony and bismuth from copper electrolyte of aforesaid present embodiment, by immersing pure copper material in copper electrolyte, the iron ion that will contact with chelating resin in the copper electrolyte is by from Fe ³⁺Ion is reduced to Fe ²⁺Therefore ion controls that impurities ionic concentration becomes very simple in the copper electrolyte.In addition, can from copper electrolyte, reclaim antimony and bismuth very efficiently.

Fig. 5 has represented the technology that the embodiment in another feature of the present invention is used.

In Fig. 5, each label representative is as follows:

1. copper electrolytic process;

2. electrolytic solution reduction process;

3. chelating resin absorption process;

4. bismuth electrolytic extraction process;

5. antimony electrolytic extraction process;

11. copper electrolyte goes out stream;

12. reduction back electrolytic solution;

13. absorb back electrolytic solution;

14. the lower concentration elutant part in the fs bismuth wash-out;

15. the lower concentration elutant part in the subordinate phase antimony wash-out;

16. the high density elutant part in the fs bismuth wash-out;

17. the high density elutant part in the subordinate phase antimony wash-out;

18. the bismuth electrolytic extraction goes out stream;

19. the antimony electrolytic extraction goes out stream;

20. bismuth metal-powder;

21. antimony metal powder.

The technology that relates to present embodiment comprises: copper electrolytic process 1, electrolytic solution reduction process 2, chelating resin absorption process 3, bismuth electrolytic extraction process 4 and antimony electrolytic extraction process 5.

Electrolytic solution reduction process 2, become reduction back electrolytic solution from copper electrolytic process 1 effusive copper electrolyte 11, and in chelating resin absorption process 3, antimony and bismuth are absorbed in the chelating resin tower, and electrolytic solution 13 is back to copper electrolytic process 1 after having removed absorption after antimony and the bismuth by absorption.

In the chelating resin tower that absorbs antimony and bismuth, flushing chelating resin and wash-out bismuth at first subsequently.At this moment, in a certain stage, the elutant 16 that will have the high density bismuth is delivered to bismuth electrolytic extraction process 4, and the elutant 14 with lower concentration bismuth is then returned Chinese blister beetle mould assembly resin tower.

After finishing the wash-out of bismuth, carry out the wash-out of antimony.At this moment, in a certain stage, the elutant 17 with high density antimony is sent to antimony electrolytic extraction process 5, and the elutant 15 with lower concentration antimony is then returned the mould assembly resin tower.

In the different stages, can carry out electrolytic extraction to elutant equally with lower concentration antimony and bismuth.

Can obtain bismuth metal powder 20 and metallic antimony powder 21 by electrolytic extraction.In addition, electrolytic extraction goes out stream 18 and 19 and turns back to chelating resin absorption process 3.

In electrolytic solution reduction process 2, Fe ³⁺Be reduced.In other words, when absorbing the antimony be present in the copper electrolyte and bismuth with chelating resin, if in copper electrolyte, have Fe ³⁺Thereby its type resin that can be chelated absorbs the quantity enable absorbed antimony and bismuth and greatly reduces.In addition, for the wash-out Fe that the type resin absorbs that is chelated ³⁺, need the hydrochloric acid of high density.Therefore, be necessary to prevent Fe ³⁺The ion type resin that is chelated absorbs.In other words, because Fe ²⁺The type that is not chelated resin absorbs, so make before electrolytic solution passes through chelating resin, it is contacted with metallic copper in being filled in post and with Fe ³⁺Ion is reduced to Fe ²⁺Ion, and then make electrolytic solution flow through chelating resin, this has just prevented Fe ³⁺Ionic absorption is to resin.

After the absorption, the water that is used to wash chelating resin is downward through by capital, thereby makes that heavier electrolytic solution is dirty continuously.Owing to compare different on the proportion with electrolytic solution, therefore removed all electrolytic solution.In this operation, can remove all electrolytic solution in the post efficiently.

Being used for be chelated antimony that the type resin absorbs and the elutriant of bismuth of wash-out is the mixture of sulfuric acid and sodium-chlor, therefore its proportion is much larger than the proportion that residues in the water in the post, like this when it flows through pillar by capital, if flow is less, mobile Fault Distribution (mal-distri bution) can appear in post inside.Therefore in order to make lighter stream waterborne, elutriant should upwards flow through pillar by the bottom.By this operation, can prevent the mixing of interior bath water of post and elutriant effectively.

Usually suppose that the antimony that chelating resin absorbed and the bismuth that are filled in the post are with SbO ⁺And BiO ⁺Form absorbed, therefore with regard to wash-out, the SbO that is adsorbed ⁺And BiO ⁺Coordination compound SbCl with chlorine ₄ ^-And BiCl ₄ ^-Form be removed, and hydrogen ion is absorbed on the absorption position of chelating resin.

Among the present invention, from chelating resin wash-out bismuth the time, used the sulfuric acid of lower concentration.This is because antimony is different for the bonding strength of chelating resin with bismuth, and passes through to use the mixture of dilute sulphuric acid and sodium-chlor, optionally the more weak bismuth of elution of bound intensity.

Use dilute sulphuric acid and sodium-chlor mixture the present invention is based on such discovery, promptly the selectivity of bismuth and antimony wash-out depends on H ⁺Concentration.In other words, by using sulfuric acid and sodium-chlor to fix Cl ^-Ion, and by adjustment of acidity or acid concentration, can be when all antimony still be fixed in chelating resin wash-out bismuth optionally.

For example, (sodium-chlor: 120 grams per liters), the weight ratio of Bi/Sb becomes greater than 10 and the selectivity grow in the elutant if use salt solution with 20 to 30 grams per liter sulfuric acid concentrations.On the other hand, if the concentration of sodium-chlor remains unchanged, and vitriolic concentration increases to 60 grams per liters, and then the weight ratio of Bi/Sb becomes 4 and selectivity forfeiture.

In addition, if use salt solution, in the selective elution of bismuth, no matter the required flow volume of elutant how with low sulfuric acid concentration, the concentration fixed of the antimony in the bismuth elutant is in 0.2 to 0.6 grams per liter and the balance that becomes, and antimony no longer wash-out go out and remain in the chelating resin.

It is 1 that hope is neutralized to the pH value with the bismuth elutriant.This is because in passing through and after the bismuth elutant removal antimony, can reduce the quantity of antimony contained in the bismuth that is reclaimed when carrying out electrolytic extraction.Separate not thoroughly not fully, if be mixed with a small amount of antimony in the bismuth elutriant, this antimony just becomes impurity in the process that reclaims bismuth from the bismuth elutant.

In the elution process of bismuth, carry out wash-out and become 0.02 grams per liter or lower reason is until the concentration of bismuth: in antimony removal process subsequently, so the bismuth of lower concentration can not become problem like this.If the bismuth wash-out is insufficient, in antimony elution process subsequently, remaining bismuth can be come out by wash-out, and the concentration of bismuth will uprise in the antimony elutant like this.

The required flow volume that is used for selectivity bismuth wash-out is BV15.In selectivity bismuth wash-out, when required flow volume reach BV6 to 7 or higher after, or in other words, if the concentration of bismuth is equal to or less than 0.5 grams per liter and the Sb/Bi weight ratio is 1 or lower in the bismuth elutant, just this elutant is reused as the elutriant in the chelating resin absorption process 3, thereby the wash-out of antimony is further suppressed.

On the other hand, with regard to the elutant in selective elution the first half of bismuth, be that required flow volume becomes BV6 elutant in the past, if the concentration of bismuth is reduced to 0.02 grams per liter or lower in the bismuth electrolytic extraction process 4, just might the selectivity bismuth wash-out in the chelating resin absorption process 3 back half, or reach BV6 or higher later part is reused this elutant in required flow volume in other words.

An important part in the antimony wash-out behind the bismuth selective elution is that the concentration of bismuth is 0.01 grams per liter or lower in the antimony elutant.By adjusting this concentration that required flow volume can obtain bismuth basically, if but increase required flow volume, the antimony that wash-out goes out in the selective elution process of bismuth has also increased, and equally also causes having in order to handle and store more elutants adding the shortcoming of this economic aspect of bigger device.

Among the present invention, if is the condition of BV14 to 15 under as described above bi concns to be adjusted into 0.02 grams per liter or lower in required flow volume by the preparation, required flow rate (SV) and the required yield temperature optimization that make elutriant, just might in the antimony wash-out, the peak concentration of bismuth in the antimony elutriant be remained on 0.01 grams per liter or lower in the capable back of taking off of selectivity bismuth in bismuth electrolytic extraction process 3.

In the antimony wash-out behind selectivity bismuth wash-out, the salt solution that uses its sulfuric acid concentration to increase to 200 to 250 grams per liters comes wash-out antimony as elutriant, like this, remains in all antimony on the chelating resin and bismuth all by wash-out.In addition, as mentioned above, in bismuth wash-out optionally, if, just may reclaim highly purified metallic antimony subsequently by the electrolytic extraction of finishing the antimony elutant if the concentration of bismuth in the bismuth washing lotion is remained below 0.02 grams per liter and the concentration of bismuth in the antimony elutant is remained below 0.01 grams per liter.

Among the present invention, reclaiming the process of antimony and bismuth from elutant, using cationic exchange membrane that anode and negative electrode are separated mutually by electrolytic extraction.This makes anode side owing to sulfuric acid is acid therefore can use cheap lead, and this makes and might carry out electrolysis and prevented anodic corrosion and wash-out, and does not have the generation of chlorine.If carry out electrolysis when anode and negative electrode are in same hydrochloric acid, then needing to use can the insoluble anode of anti-the chlorating, as DSA, and will handle the chlorine of generation.

Because the rising with electrolysis temperature exists the tendency that current efficiency increases, the electrolytic extraction of bismuth and the electrolytic extraction of antimony are different.In addition, because the overvoltage of electrolytic deposit must improve the current density that is used for bismuth slightly, and think 20 to 50A/m ²Current density be best.Therefore, for the electrolytic extraction of bismuth, the constant-current electrolysis under the high temperature is best.

In the electrolytic extraction process of antimony, even under the condition of the density loss of antimony, also do not have the change of electric current when using constant-current electrolysis in elutant, if therefore electric current flows same as before, then electrolysis temperature raises and current efficiency descends.In addition, be difficult to determine when electrolysis is finished, and need to observe continuously the concentration of antimony in the elutant.

If under constant voltage, carry out electrolysis, if then in the elutant density loss voltage of antimony increase and electric current stops to flow, then produce hydrogen from negative electrode, therefore determine the decline when current efficiency was finished and can be prevented in electrolysis easily.

In the electrolytic extraction of antimony, think that why can observe this trend that current efficiency descends is because the antimony elutant has the sulfuric acid and the sedimentary antimony of 200 to 250 grams per liter high densitys has dissolved again.Therefore, be necessary to carry out at low temperatures electrolysis, be preferably between 10 to 25 degrees centigrade, and the low-voltage electrolysis under the low temperature is best for the electrolytic extraction of antimony.

In the wash-out of antimony, if the elutant of antimony with high density antimony is carried out electrolytic extraction, and the elutant that will have the antimony of lower concentration antimony is back into chelating resin as elutriant, then only needs the single-stage electrolyzer for electrolytic extraction.

But, if stibiated solution is used as elutriant again, the quantity that then remains in the antimony on the chelating resin has increased, and it has produced disadvantageous effect to absorption equilibrium.

Therefore, reasonable is that the elutant with lower concentration antimony is carried out electrolytic extraction, and the two-level concatenation of wherein recommending to have better current efficiency is used for electrolysis.

Because the antimony concentration in the first step of cascade is higher, might carry out constant-potential electrolysis under the higher voltage relatively.

Then the antimony elutant that goes out stream and have low antimony concentration of the first step is sent into the second stage of cascade.Because antimony concentration is lower, even under high pressure carry out constant-potential electrolysis, it is lower that electric current still keeps.Therefore, recommend to carry out under low pressure constant-potential electrolysis to finish electrolysis efficiently.

Use this method, the antimony elutant directly also can be delivered to two electrolyzers continuously, and can compare the reservation comparatively small amt of solution like this with common ion exchange method directly with from the multiplexing elutriant of doing of the effusive solution weight of second stage electrolyzer.

Fig. 6 has represented to be used for the schematic drawing of the bismuth electrolyzer 20 of electrolytic extraction process.

In Fig. 6, each label representative is as follows: 21. lead electrodes; 22. niobium electrode or titanium electrode; 23.200 the sulphuric acid soln of grams per liter; 24. bismuth elutant; 25. cationic exchange membrane.

This electrolyzer 20 has chloride plate 21 and niobium or titanium negative plate 22, and it is separated by cationic exchange membrane 25, make sulfuric acid remain on anode side, and bismuth elutant 24 remains on cathode side.Hydrogen ion can pass through cationic exchange membrane 25, and chlorion can not.

Among the present invention, the reason of using niobium or titanium negative electrode is that it can corrosion-resistant well and chlorination in hydrochloric acid, and because can easily remove electro-deposition from it.

In addition, the oxide compound of these electrode surfaces can play the effect of catalyzer in electrodeposit.

Embodiment 36

In post, insert 1 liter of chelating resin (Epolas MX-2, make by the Miyoshi oil company), and make its antimony concentration be 0.5 to 0.6 grams per liter and bi concns be the copper electrolyte of 0.3 to 0.4 grams per liter under 60 degrees centigrade, flow through be filled with metallic copper pillar with the reduced iron ion, subsequently after this has absorbed the chelating resin of antimony and bismuth with the hot wash of BV3, use the mixture of sulfuric acid and sodium-chlor and make its by capital downwards by this post with wash-out bismuth optionally.The condition of wash-out is shown among 6-1 and the table 6-2 with the results are shown in.

As show shown in 6-1 and the 6-2, when sulfuric acid concentration is 60 grams per liters or when higher, antimony is gone out by wash-out, has lost the selectivity between antimony and the bismuth thus, thereby can not the selective elution bismuth.In addition, even when sulfuric acid concentration is low to moderate 30 grams per liters, be wash-out antimony optionally still under the 180 grams per liter conditions at sodium chloride concentration.The optimum concn of elutriant is the sulfuric acid of 30 grams per liters and the sodium-chlor of 120 grams per liters, if but using its sulfuric acid concentration is that the solution that 60 grams per liters or lower and its sodium chloride concentration are no more than 180 grams per liters carries out wash-out, just can suppress the wash-out of antimony and optionally wash-out go out bismuth.

Embodiment 37

After antimony and bismuth being absorbed resin by the same way as of being done in as embodiment 36, for optionally and efficiently wash-out antimony and bismuth, use the combination of antimony and bismuth elution requirement, and by be downward through the mixture of sulfuric acid and sodium-chlor by capital, bismuth is by wash-out at first, follows wash-out by antimony.Elution requirement is shown among 7-1 and the table 7-2 with the results are shown in.As show shown in 7-1 and the table 7-2, in the wash-out of antimony, even sulfuric acid concentration is 200 grams per liters,, also reduced the amount of the antimony that wash-out goes out if sodium chloride concentration is low to moderate 60 grams per liters.In the wash-out of antimony, if conditions permit remains in all antimony on the chelating resin and bismuth entirely by wash-out, therefore this just preferably carry out wash-out under the condition of sulfuric acid that high density is arranged and sodium-chlor.But, solution is limited to the sulfuric acid of 250 grams per liters and the sodium-chlor of 150 grams per liters, and if concentration ratio this is also high, can reach capacity state and being precipitated out of sodium-chlor.In the antimony wash-out, concerning the sulfuric acid concentration of 200 to 250 grams per liters, sodium chloride concentration is 120 to 150 grams per liters preferably, and can see that in this case the eluting rate of antimony is 80% or higher.

Embodiment 38

By the same way as of being done in as embodiment 36 antimony and bismuth are being absorbed to resin, adopt with embodiment 36 in used identical elution process, use comes wash-out to become 15 up to BV with the elutant that SV1.5 flows through the sulfuric acid concentration with 180 grams per liter sodium chloride concentrations and 30 grams per liters of pillar by the bottom.

Fig. 7 has represented the elution curve that is used for comparison that elutant flow through obtain by capital by under 40 and 50 degrees centigrade.

Fig. 8 has represented by the elution curve at the present embodiment that elutant is flow through at the bottom of by post under 50 and 60 degrees centigrade to obtain.

Table 8-1 and 8-2 represent the eluting rate for antimony under every kind of condition and bismuth.

As shown in Figure 7, when elutriant was downward through by capital under 50 degrees centigrade, the curve high density partly showed: compare when being flowed down by capital under 40 degrees centigrade with elutriant, 5% raising is only arranged; Yet 50 degrees centigrade dirty out-of-date, the position of concentration peak is come early.Therefore, elutriant is as at high temperature flowing through as can be seen, and then wash-out is more effective.

As can be seen, compare when pillar and elutriant are downward through pillar by the top if elutriant is upwards flow through by the bottom in table 8-1 and 8-2, the concentration of curve high density part has improved 25%.In addition, when the effluent volume that flows through reached BV6, bismuth was almost gone out by complete wash-out, and when beginning to flow through pillar by the top with elutriant relatively, by making elutriant can cut down the effluent volume that must flow through pillar, make wash-out more effective like this by the bottom pillar that begins to flow through.

As among Fig. 8 as can be seen, when under 60 degrees centigrade, making elutriant flow through pillar, relatively, can see 30% raising when under 50 degrees centigrade, flowing through pillar in the high density part with elutriant.Therefore make elutriant under 60 degrees centigrade, can more effectively finish wash-out by pillar.

8-1 and 8-2 are difficult to find out by table, the eluting rate of any condition bismuth there is any difference, but relies on these conditions, and by making the bi concns in the bismuth elutant with high bi concns higher, the electrolytic extraction that will describe below can more effectively finishing.

Wish high temperature with regard to required yield temperature, and think that 40 degrees centigrade or higher temperature are best, but consider cost and the container material that improves the elutriant temperature, then exist some restrictions.In addition, when elutriant at high temperature began by pillar by the bottom, the eluting rate of antimony tended to increase.But, when considering the peak concentration of bismuth, if elutriant is begun by pillar by the bottom under 60 degrees centigrade, then the concentration of bismuth is the highest and may carry out wash-out with less column volume.In addition, by reducing amount, may reduce the eluting rate of antimony by the elutriant of pillar.

Can find by these results, make elutriant under 40 to 60 degrees centigrade, begin to come the wash-out bismuth, can carry out wash-out effectively by pillar by the bottom by the volume that adopts BV10.

Embodiment 39

By with embodiment 38 in do identical mode wash-out bismuth after, make elutriant by pillar and wash-out antimony with sodium-chlor that sulfuric acid that concentration is 250 grams per liters and concentration is 150 grams per liters.

Fig. 9 represents by making elutriant begin to flow through the elution curve that pillar obtains by the column bottom under 50 and 60 degrees centigrade.

Table 9-1 and 9-2 have represented for the antimony of every kind of condition and the eluting rate of bismuth.

As among Fig. 9 as can be seen, when elutriant begins by pillar by the bottom under 60 degrees centigrade, with elutriant 50 degrees centigrade during down by pillar relatively, in the high density part of curve, concentration has 10% raising.In addition, find out by the result shown in table 9-1 and the 9-2, as in the bismuth wash-out, when elutriant when passing through pillar within 40 to 60 degrees centigrade the scope, can carry out wash-out more efficiently.In addition, the bismuth if any 2 to 5 grams per liters in the bismuth wash-out remains in the resin, then its in ensuing antimony elution process by wash-out and lost selectivity thus.

Find that thus if the wash-out bismuth is 0.02 grams per liter or lower until the ultimate density of bismuth in the bismuth elution process, in the antimony elution process, the concentration of bismuth just is 0.01 grams per liter or lower in the antimony elutant subsequently.

In addition, in the elution process of bismuth, wash-out back half, in other words the required flow volume of elutriant reach BV8 or higher after solution (bismuth＜0.5 grams per liter, antimony: 0.20 to 0.25 grams per liter) be recycled and reused for the first half of wash-out.On the other hand, have 0.02 grams per liter or the lower antimony and the solution of bi concns, find that then the ratio of antimony left in the bismuth elution process increases to some extent if use in half at wash-out back.

Embodiment 40

Using the mixture of the sodium-chlor of the sulfuric acid of 20 grams per liters and 120 grams per liters is 0.02 grams per liter or lower so that go up the wash-out bismuth from the chelating resin (Epolas MX-2, Miyoshi makes) that has absorbed antimony and bismuth until the ultimate density of bismuth.

Next, with in the sodium hydroxide of 200 grams per liters and the elutant of gained (antimony: 0.24 grams per liter, bismuth: be 1 5.3 grams per liters) until its pH value, after removing throw out, use as shown in Figure 6 electrolyzer and by use 30A/m ²Current density carry out constant-current electrolysis and reclaim bismuth.Gained the results are shown among table 10-1 and the 10-2.For relatively, provided equally and do not adjusted the pH value and situation when carrying out electrolytic extraction.

As show as shown in 10-1 and the 10-2, by in and elutriant to pH value be 1, can reduce the concentration of antimony and reduce the quantity of the antimony that is contained in the bismuth of recovery.

Embodiment 41

In the wash-out operation of embodiment 40, after wash-out goes out bismuth, use the mixture of 250 grams per liter sulfuric acid and 150 grams per liter sodium-chlor to come wash-out antimony.

Next, (antimony: 2.8 grams per liters, bismuth: 0.009 grams per liter) be neutralized to the pH value is 1 to 3 to the sodium hydroxide solution by adding 200 grams per liters with the antimony wash solution of gained.

Gained the results are shown among table 11-1 and the 11-2.Provided equally by being hydrolyzed and the result when adding distilled water and sodium hydroxide at the same time.

From showing 11-1 and 11-2 as can be seen, become 0.02 grams per liter or lower by the ultimate density that in the bismuth elution process, makes bismuth, in the antimony elutant, just almost there has not been residual bismuth subsequently.

In addition, if the concentration of bismuth is 0.02 grams per liter or lower in the antimony elutant, the amount of residual bismuth is equally very low in the antimony of Hui Shouing subsequently.

In addition, in order to obtain high purity antimony, this elutant that can neutralize to pH value is 1 or is hydrolyzed, but exists the problem that the quantity of salvage material will reduce.If antimony is to be settled out in 3 o'clock in the pH value, the quantity of institute's salvage material is bigger, yet if the concentration of bismuth is higher in the antimony elutant, the amount of contained bismuth is high equally in the antimony that reclaims.Therefore, need to reduce the concentration of bismuth in the antimony elutriant.

Embodiment 42

In electrolyzer as shown in Figure 6, (negative electrode and anode are 65mm * 60mm) to use the negative electrode of niobium system and the anode of plumbous system, and with cationic exchange membrane (Neoscep-tor, make by Tokuyama Sotatsu company limited) they are separated, wherein the distance of a film and a battery lead plate is 30mm.In negative electrode one side, use the bismuth elutant that obtains by the bismuth wash-out among the embodiment 36, and in anode side, working concentration is that the sulfuric acid of 200 grams per liters is finished the bismuth electrolysis.

Table 12 has been represented the relation between electrolysis temperature, current density and the current efficiency.

As shown in Table 12, under same current density, current efficiency improves when electrolysis temperature is high.In addition, under identical electrolysis temperature, current efficiency improves with the increasing of current density.Found that from these: the electrolytic extraction of bismuth, wish to have 40 degrees centigrade or higher temperature and 50A/m ²Current density.But, with regard to temperature, as described in embodiment 38, temperature be 60 degrees centigrade or low be best.The purity of bismuth is 98% or higher herein.

Embodiment 43

In the wash-out of antimony,, come the wash-out bismuth by the condition of table 13 expression for the ultimate density that makes bismuth in the bismuth elution process is 0.02 grams per liter or lower.

As in the table 13 as seen, carry out wash-out by elutriant with sodium chloride concentration with the sulfuric acid concentration of 20 grams per liters and 180 grams per liters, the concentration that just can make bismuth in the antimony elutant is 0.01 grams per liter or lower.In addition, use the elutriant of the sodium chloride concentration of sulfuric acid concentration with 20 grams per liters and 120 grams per liters, by improving the volume BV of required flow of solution, just can make bi concns is 0.01 grams per liter or lower.But, improve required flow volume BV and need handle a large amount of solution.In addition, though used elutriant when increasing required flow volume BV,, still be necessary to reduce required flow volume BV in order to increase the volume of antimony wash-out with 20 grams per liter sulfuric acid concentrations and 180 grams per liter sodium chloride concentrations.

Use is 0.01 grams per liter or lower elutant by the bi concns that wash-out obtained under these conditions, carries out constant-current electrolysis by using the electrolyzer shown in Fig. 6 at normal temperatures by the same procedure described in the embodiment 42.The results are shown in the table 14.

As shown in table 14, be 0.01 grams per liter or lower elutant by using bi concns, also can obtain 99.5% or higher high purity antimony even under high current density, carry out electrolysis.

In other words, concentration by bismuth in the maintenance antimony elutant is 0.01 grams per liter or lower, can obtain high purity antimony by electrolysis, and when electrolysis finishes, can make the antimony concentration in the solution reduce to 0.05 grams per liter or lower, this final solution just can turn back in back half wash-out in the chelating resin like this.

Embodiment 44

As the way use electrolyzer as shown in Figure 6 of embodiment 42, and the antimony wash solution of the bi concns of antimony concentration with 5.1 grams per liters that is obtained in the antimony elution process of use by embodiment 37 and 0.1 grams per liter, at 30A/m ²Current density and the electrolysis temperature of 10 degrees centigrade, 25 degrees centigrade and 40 degrees centigrade under carry out electrolysis.Table 15 shows the relation of electrolysis temperature and current efficiency.

As shown in table 15, current efficiency reduces with temperature and increases.This is because the antimony wash solution has the high sulfuric acid concentration of 250 grams per liters, so make the current efficiency step-down because the antimony that the temperature rising has precipitated dissolves again.

Can find from these results: for the electrolytic extraction of antimony, 40 degrees centigrade or lower temperature are fit to, and if its in 10 to 25 degrees centigrade scope, just can obtain 50% to 100% current efficiency.

Embodiment 45

Suppose by using the electrolyzer as shown in Fig. 6 as doing among the embodiment 42, then the antimony elutant that is obtained in antimony elution process 37 directly is provided to cathode side from pillar, and hypothesis uses 2 grades of cascade electrolyzers, and the solution that then will have a bi concns of the antimony concentration of 2.08 grams per liters and 0.005 grams per liter is delivered to first step electrolyzer and carry out the first step electrolysis of antimony under constant voltage and 40 degree centigrade.Next, the solution that will have a bi concns of the antimony concentration of 0.89 grams per liter and 0.0097 grams per liter is delivered to second stage electrolyzer and carry out second stage electrolysis under 40 degrees centigrade and constant voltage.Gained the results are shown among table 16-1 and the 16-2.Embodiment adopts 30A/m as a comparison ²And 50A/m ²Current density carry out electrolytic extraction, the result is shown among table 16-1 and the 16-2 equally.

As show as shown in 16-1 and the 16-2, in the electrolytic first step, the current efficiency of constant-potential electrolysis is than the height of constant-current electrolysis.In addition, in the electrolytic second stage, when under 1.8 volts, carrying out electrolysis, obtained high current efficiency.Descend because current efficiency strengthens with voltage, so the voltage that adopt the electrolytic second stage is the best at 1.8 to 2.0 volts.

Can find the electrolytic extraction of antimony from these results, can more effectively finish extraction by carrying out constant-potential electrolysis.

Embodiment 46

By same procedure as being done among the embodiment 36, the solution of the sodium-chlor of the sulfuric acid of use 20 grams per liters and 180 grams per liters begins to flow through pillar with it by the bottom under SV0.5 under 60 degrees centigrade, so that the wash-out bismuth is BV15 until required flow volume from the pillar that has absorbed antimony and bismuth.The solution of the sodium-chlor of the sulfuric acid of use 250 grams per liters and 150 grams per liters upwards flows through pillar by the bottom so that wash-out antimony is BV15 up to required flow volume with it under SV1.5 under 60 degrees centigrade subsequently.

In the electrolyzer as shown in Fig. 6 of embodiment 42, use the bismuth wash solution that is obtained by the bismuth elution process the high density part (bismuth: 1.74 grams per liters, antimony: 0.07 gram. rise required flow volume: BV2 to 5) and at 40 degrees centigrade adopt 20A/m down ²Current density carry out electrolytic extraction.

In addition, press Same Way, high density part (the antimony: 3.43 grams per liters, bismuth: 0.01 grams per liter, required flow volume: of the antimony elute soln that use is obtained by the antimony elution process BV2 to 6) in first step electrolyzer, to carry out electrolytic extraction continuously for 2.2 volts with constant voltage under 25 degrees centigrade.

In addition, make the stream that of first step constant-potential electrolysis groove become 7 the parts that wash out of antimony elution process to 15 after with required flow volume BV and flow to the second stage electrolyzer of 1.8 volts of constant voltages of employing continuously and carry out electrolytic extraction.Gained the results are shown in table 17-1 and 17-2.

From the result who is shown in table 17-1 and 17-2, can find, by finishing the ultimate density that the antimony wash-out can make bismuth in the bismuth elution process in the above conditions is 0.02 grams per liter or lower, and may to make the peak concentration of bismuth in the antimony elution process be 0.01 grams per liter or lower.

In addition, reach BV5 to 6 or higher (lower concentration elutant) elutant part afterwards in required flow volume, concentration and antimony the concentration in antimony elution process of bismuth in the bismuth elution process is 0.5 grams per liter or lower and can reuse this elutant part same as before in wash-out the first half.

By in carrying out electrolytic extraction, using, can under 50% current efficiency, make the ultimate density of bismuth reduce to 0.02 grams per liter in the above conditions by the high density part of the bismuth wash solution that is obtained in the bismuth elution process.In addition, this electrolytic go out stream can return the bismuth wash-out back half.

By using the antimony wash solution obtained by the antimony elution process in the above conditions to carry out second stage electrolytic extraction continuously, can be under 70% current efficiency ultimate density be reduced to 0.02 grams per liter.In addition, this electrolytic go out stream can be recycled and reused for the antimony wash-out back half.

Embodiment 47

Use electrolyzer as shown in Figure 6, anode side contains the sulphuric acid soln of 200 grams per liters, and cathode side to contain antimony concentration be 4.3 grams per liters and bi concns is the sulfuric acid of 6.6 grams per liters and the mixture of sodium-chlor, and under 2.2 volts conditions with normal temperature, carry out constant-potential electrolysis.The antimony that is reclaimed is 41.0% and the bismuth that reclaimed is 52.6%, and current efficiency is 57.1%.

Figure 10 has represented the relation between the antimony and bismuth in electric current flowing time and the elutant.

As shown in Figure 10, can find that the concentration of antimony and bismuth descended along with the electric current mobile time, and metal deposition can reclaim from elutant also on negative electrode.

The grating of antimony and bismuth depend on before the electrolysis its in elutant concentration and change.

In addition, if the concentration ratio of antimony/bismuth is 1: 1 in the elutant, the level proportioning of salvage material then, antimony/bismuth also is 1: 1.

Table 6-1

Sulfuric acid sodium-chlor BV SV eluting temperature

(grams per liter) (grams per liter) (degree centigrade) 1 30 120 15 3.0 402 60 120 16 3.0 403 100 180 20 3.0 404 30 180 10 3.0 405 30 120 10 3.0 506 30 120 15 1.5 507 30 180 20 1.5 508 20 120 10 0.5 60

Table 6-2 antimony uptake bismuth uptake antimony eluting rate bismuth eluting rate wash-out goes out, (grams per liter resin), (grams per liter resin), (%), (%) quantity is than 1 40.04 27.49 5.3 95.4 12.262 34.89 24.45 18.0 100.0 3.893 33.91 24.92 85.8 89.5 0.854 36.65 27.22 15.5 97.1 4.665 37.65 25.20 5.8 99.0 11.456 33.65 25.78 9.0 91.8 7.847 29.53 14.55 23.7 100.0 2.088 27.42 18.63 6.0 73.5 8.30

Table 7-1

Sulfuric acid sodium-chlor BV SV eluting temperature, (grams per liter), (grams per liter), (degree centigrade) 11 100 180 10 3.0 4,012 200 60 10 3.0 4,013 200 120 10 3.0 5,014 200 120 15 1.5 5,015 250 150 20 1.5 5,016 250 150 15 1.5 60

Table 7-2

Bismuth elution process antimony elution process remains in the quantity quantity ratio of bismuth on the quantity that resin remains in the upper antimony that resin antimony eluting rate bismuth eluting rate wash-out goes out, (grams per liter resin), (grams per liter resin), (%), (%) 11 28.62 4.85 77.9 100.0 4.6012 30.98 0.80 15.4 100.0 5.8513 35.47 0.24 78.0 100.0 115.3014 30.63 2.11 100.0 25.1 57.7915 21.80 0.11 79.0 100.0 191.616 25.77 4.93 83.3 16.2 26.8

Table 8-1

The bismuth elution process

(sulfuric acid 30 grams per liters, sodium-chlor 180 grams per liters) the required yield temperature antimony of required flow direction eluting rate bismuth eluting rate

(degree centigrade) (%) (%) begin 50 16.3 99.4 the end of by and begin 50 24.0 99.5 the end of by by backing down the beginning 50 23.7 96.1 by backing down the beginning 40 15.5 94.5

The required flow direction bismuth of table 8-2 peak concentration antimony mean concns

(grams per liter) (grams per liter) begins 16.4 0.40 the end of by and begins 21.0 0.65 the end of by by backing down the beginning 13.0 0.25 by backing down the beginning 12.4 0.20

Table 9-1

The bismuth elution process

The bismuth ultimate density of the remaining bismuth of (sulfuric acid 30 grams per liters, sodium-chlor 180 grams per liters) remaining antimony of required flow direction eluting temperature BV

Per-cent per-cent

(degree centigrade), (%), (%), (grams per liter) begins 50 20 73.8 0.7 0.21 by backing down the beginning 60 10 73.6 30.0 0.65 by backing down the beginning by backing down, (1) 60 15 82.1 5.3 0.13 begins 50 10 70.6 20.5 0.82 the end of by begins 60 15 75.6 0.6＜0.01 the end of by and is begun the end of by, (2) 60 15 88.7 9.6 0.02, (1) reuses the eluate that antimony concentration is 0.2 grams per liter, (2) reuse the eluate that antimony concentration is 0.25 grams per liter

Table 9-2

Antimony elution process (SV1.5)

The antimony eluting rate bismuth eluting rate required flow direction of bismuth Cmax (%) (3) (%) (grams per liter) begins 99.0 100.0 0.15 to begin 83.0 16.2 0.82 to begin 89.9 32.9 0.98 the end of by and begin 100.0 100.0＜0.01 the end of by and begin (2) 96.4 100.0 0.01 (1) eluting rates when reusing the eluate that antimony concentration is 0.2 grams per liter (2) and reusing percentage that the eluate that antimony concentration is 0.25 grams per liter (3) stays the bismuth in the bismuth elution process when setting and be 100 end of by by backing down the beginning (1) 94.7 100.0 0.15 by backing down by backing down

Table 10-1

After initial soln pH adjusts

Antimony (gram) bismuth (gram) antimony (gram) bismuth (gram) pH adjusts 0.24 5.53 0.14 5.00 no pH and adjusts 0.30 2.80--

Table 10-2

The grating of salvage material (%) behind the electrolytic extraction

Antimony (gram) bismuth (gram) antimony bismuth oxygen pH adjusts 0.015 0.53 2.7 87.0 6.7

44.6 14.2 18.0 no pH adjust 0.033 0.33 8.5 82.4 3.3 by the neutralization deposition

Table 11-1

The processing pH antimony that reclaims after initial soln is processed, (gram) bismuth, (gram) antimony, (gram) bismuth, (gram) material, be hydrolyzed 1 3.00 0.010 1.86 0.0062 1.20 water+NaOH 2 3.04 0.011 0.87 0.0032 2.28 water+NaOH 3 3.04 0.011 0.16 0.0015 3.01 with 3 1.42 0.0045 0.13 0.0031 2.10 in (gram) and in 1 1.42 0.0045 0.59 0.0052 0.86 and in 2 1.42 0.0045 0.21 0.0043 1.74

Table 11-2

The grating of salvage material (%) is handled in the antimony bismuth oxygen and in 72.1 0.04 17.0 and in 73.4 0.13 17.0 and 74.0 0.33 17.0 hydrolysis, 72.5 0.03 17.0 water+sodium hydroxide 73.5 0.15 17.0 water+sodium hydroxide 74.0 0.31 17.0

Table 12 bismuth starting point concentration electrolysis temperature current density bismuth ultimate density current efficiency (%) (grams per liter) (degree centigrade) (A/m ²) (grams per liter) 5.10 10 20 0.58 57.55.10 10 40 0.42 59.05.10 10 50 0.53 67.01.74 10 30 0.49 39.01.74 25 30 0.33 45.51.74 40 30 0.38 44.5

Table 13

(g/l) concentration 20 120 16 0.034 2.57 0.02220 120 10 0.12 1.64 0.07420 180 30 0.0062 9.80 0.006520 180 20 0.0054 7.01 0.006420 180 15 0.0056 5.09 0.0039 of (grams per liter resin) (grams per liter) bismuth of (grams per liter) (grams per liter) in the SV0.5 sulfuric acid sodium chloride BV bismuth ultimate density antimony elution amount antimony eluate

Table 14 current density antimony ultimate density bismuth ultimate density bi content (%) antimony purity (%) (A/m ²) (grams per liter) (grams per liter) 20 0.04 0.009 0.42 99.6 30 0.02 0.007 0.23 99.8 50 0.05 0.007 0.22 99.8

Table 15 electrolysis temperature (degree centigrade) current efficiency (%)

10 98.5

25 62.0

40 47.0

Table 16-1

Average voltage (volt) mean current

Density

(A/m ²) cascade first step voltage rating 2.2V-37.5

Rated current 30A/m ²2.19-

Rated current 50A/m ²2.22-cascade second stage voltage rating 1.8V-7.1

2.0V - 15.1

2.2V - 33.0

2.5V - 65.7

Table 16-2

Antimony concentration bi concns finally

Stream efficient

(%) cascade voltage rating of (grams per liter) (grams per liter) 2.2V 0.68 0.033 59.2 first step rated current 30A/m ²0.38 0.01 34.0

Rated current 50A/m ²0.33 0.66 37.0 cascade voltage rating 1.8V, 0.32 0.009 84.3 second stage 2.0V 0.27 0.007 41.6

2.2V 0.07 0.008 25.4

2.5V 0.04 0.005 13.1

Table 17-1

Elution process

Eluting rate lower concentration side

Antimony bismuth antimony concentration bi concns bismuth ultimate density bismuth peak concentration

(%) (%) (grams per liter) (grams per liter) (grams per liter) (grams per liter) first step 16.1 99.6 0.40 0.10 0.02-second stage 81.2 0.4 0.35 0.003-0.01

Table 17-2

The electrolytic extraction process

Ultimate density

Antimony (grams per liter) bismuth (grams per liter) current efficiency (%) first step 0.0033 0.0054 50.9 second stage 0.02 0.007 69.6

In the present invention, use the mixture of sulfuric acid and sodium-chlor so that from the chelating resin that has absorbed antimony the copper electrolyte and bismuth, optionally reclaim antimony and bismuth, and can reclaim these metals by electrolysis.In addition, by before electrolysis, adjusting the pH value, can improve the antimony that reclaimed and the purity of bismuth.

Claims (34)

1. comprise a kind of of following steps: in order to reduce Fe by the method that reclaims antimony and bismuth in the copper electrolyte ³⁺Ion and in the copper electrolyte of impure antimony, bismuth and iron, immerse copper product, the redox-potential of copper electrolyte is adjusted to less than 650 millivolts, in order to absorb antimony and bismuth copper electrolyte is contacted with chelating resin, and elutriant is contacted with chelating resin, with wash-out and reclaim antimony and bismuth.

According to claim 1 reclaim the method for antimony and bismuth by copper electrolyte, wherein copper product is made bulk, sheet and one of Powdered shape.

3. according to the method by copper electrolyte recovery antimony and bismuth of claim 1 or 2, wherein elutriant is selected from sodium chloride-containing and vitriolic solution and contains thiocarbamide and vitriolic solution.

4. according to the method by copper electrolyte recovery antimony and bismuth of claim 3, wherein sodium chloride-containing and vitriolic solution have the sodium chloride concentration of 60 to 180 grams per liters and the sulfuric acid concentration of 30 to 200 grams per liters, and wherein temperature is 10 to 60 degrees centigrade.

5. according to the method by copper electrolyte recovery antimony and bismuth of claim 3, wherein contain thiocarbamide and vitriolic solution and have the thiourea concentration of 5 to 20 grams per liters and the sulfuric acid concentration of 25 to 300 grams per liters, and wherein temperature is 25 to 60 degrees centigrade.

6. a kind of method by copper electrolyte selective recovery antimony and bismuth that comprises following steps: (1) contacts with metallic copper by making copper electrolyte, will be present in the Fe in the copper electrolyte ³⁺Ion is reduced to Fe ²⁺Ion.(2) by the reducing solution that is obtained in the step (1) is contacted with chelating resin antimony in the electrolytic solution and bismuth are absorbed to chelating resin.(3) with this chelating resin of hot water injection.(4) by under 40 to 60 degrees centigrade, making the sulfuric acid that comprises 20 to 30 grams per liters contact the wash-out bismuth to obtain the elutant of bismuth with the chelating resin that washed with the elute soln of the bismuth of the mixture of the sodium-chlor of 120 to 180 grams per liters.(5) behind the wash-out bismuth, the antimony elute soln and the chelating resin of the mixture of the sodium-chlor by making the sulfuric acid that comprises 100 to 250 grams per liters and 120 to 180 grams per liters between 40 and 60 degrees centigrade contact wash-out antimony to obtain the elutant of antimony.

7. according to the method for the selective recovery of claim 6, wherein when being contacted with chelating resin, used copper electrolyte a pillar.

8. according to the method for the selective recovery of claim 6 or 7, wherein by making the antimony elute soln come wash-out antimony by this pillar by the bottom.

9. according to the method for the selective recovery of claim 6 or 7, wherein by making bismuth precipitation liquid come the wash-out bismuth by this pillar by the bottom.

10. according to the method for the selective recovery of claim 6 to 8, wherein using the bi concns that obtains in the bismuth elution process in the bismuth elution step is that 0.5 grams per liter or lower bismuth elutant part are as the bismuth elutriant.

11. according to the method for the selective recovery of claim 6 to 9, wherein to use the bi concns that is obtained in bismuth electrolytic extraction step in half be 0.02 grams per liter or lower go out the stream part as the bismuth elute soln at bismuth elution step back.

12. according to the method for claim 6 to 10, wherein the stream part that goes out that will have 0.02 grams per liter or lower antimony concentration in half at bismuth elution step and/or antimony elution step back is returned as elute soln.

13. according to the method for claim 6 to 11, wherein making elutriant is 0.02 grams per liter or lower by the concentration of pillar bismuth in wash solution.

14. method by a kind of selective recovery of electrolytic extraction, wherein anode is separated each other with negative electrode by cationic exchange membrane, and wherein will place cathode side and sulfuric acid is placed anode side as the sulfuric acid tank liquor as bismuth electrolytic solution by the bismuth wash solution that method obtained of claim 6, and wherein the bismuth in the bismuth electrolytic solution with the form of bismuth metal by electrolytic extraction.

15. according to the method for the selective recovery of passing through electrolytic extraction of claim 14, wherein use bismuth wash solution with 0.5 grams per liter or higher bi concns as bismuth electrolytic solution and 20 to 50A/m ²Use constant-current electrolysis to carry out electrolytic extraction concentration of bismuth in electrolytic solution down and become 0.02 grams per liter or lower.

16. pass through the method for the selective recovery of electrolytic extraction, wherein anode is separated each other with negative electrode and wherein will place cathode side and sulfuric acid is placed anode side as the sulfuric acid tank liquor as antimony electrolytic solution, and wherein reclaim antimony in the antimony electrolytic solution with the form of metallic antimony by electrolytic extraction by the antimony wash solution that method obtained of claim 6 by cationic exchange membrane.

17. according to the method for the selective recovery of claim 16, wherein the electrolysis temperature in antimony electrolytic extraction step is 40 degrees centigrade or lower.

18. according to the method for the selective recovery of claim 16 and 17, wherein electrolysis step comprises that bath voltage maintains 2.2 to 2.5 volts first step electrolytic process and bath voltage and maintains 1.8 to 2.0 volts second stage electrolytic process.

19. method according to the selective recovery of claim 18, wherein will have 20 or the antimony wash solution of higher antimony/bi concns ratio be used for first step electrolytic process with this electrolytic extraction antimony, and wherein the stream that goes out of first step electrolytic process is used for second stage electrolytic process.

20. according to the method for the selective recovery of claim 19, the antimony wash solution that wherein will have the antimony/bi concns ratio less than 20 is used for second stage electrolytic process.

21. comprise a kind of method by selective recovery antimony in the copper electrolyte and bismuth of following steps: (1) contacts by the metallic copper in making cupric electrolysis solution and being filled in post and will be present in Fe in the copper electrolyte ³⁺Ion is reduced to Fe ²⁺Ion.(2) chelating resin in making the copper electrolyte that obtained in the step (1) and filling in post contact with this and absorbs antimony in the copper electrolyte and bismuth also subsequently by making hot water be begun to wash chelating resin in the post by pillar by the top.(3) be that 20 to 30 grams per liters and sodium-chlor are that the elute soln of 120 to 180 grams per liters comes from the chelating resin that has absorbed antimony and bismuth step (2) optionally wash-out bismuth by chelating resin by under 40 to 60 degrees centigrade, making sulfuric acid.(4) by make under 40 to 60 degrees centigrade sulfuric acid be 100 to 250 grams per liters and sodium-chlor be 120 to the elute soln to 180 grams per liters come by chelating resin wash-out in step (3) wash-out remaining antimony on the chelating resin of bismuth.

22. the method according to the selective recovery of claim 21 wherein makes the elute soln of sulfur acid and sodium-chlor be begun to come the wash-out bismuth by pillar by the bottom.

23. the method according to the selective recovery of claim 21 wherein makes the elute soln of sulfur acid and sodium-chlor be begun to come wash-out antimony by pillar by the bottom.

24. method by electrolytic a kind of selective recovery, wherein use cationic exchange membrane that anode is separated each other with negative electrode and wherein form the sulfuric acid tank liquor, reclaim bismuth metal or metallic antimony so that in by bismuth elute soln that is obtained in the claim 21 or antimony elute soln, finish electrolysis at cathode side.

25. the method for a selective recovery is wherein reused bi concns that claim 21 obtains and is 0.5 grams per liter or lower wash solution as elutriant in the first half of wash-out.

26. the method for a selective recovery, wherein the bi concns in going out the stream part becomes 0.02 grams per liter or when lower, and this electrolysis that claim 21 is obtained goes out the stream part and returns with as the wash-out of claim 21 back used elutriant in half.

27. the method for a selective recovery, wherein the antimony concentration in going out stream becomes 0.02 grams per liter or when lower, and this that claim 21 is obtained goes out the stream part and returns with as the bismuth of claim 21 or antimony wash-out back used elutriant in half.

28. the method for the selective recovery of claim 21, wherein making elute soln is 0.02 grams per liter or lower by pillar until the concentration of bismuth, and the concentration of antimony becomes 0.01 grams per liter or lower in the antimony elutant that the method by claim 21 of making like this obtains.

29. by a kind of recovery method of electrolytic extraction, wherein the concentration by bismuth in the bismuth wash solution that method obtained of claim 21 is 0.5 grams per liter or higher, and this bismuth wash solution is carried out 20 to 50A/m ²The concentration of constant-current electrolysis bismuth in electrolytic solution be 0.02 grams per liter or lower.

30. by the method for a kind of selective recovery of electrolytic extraction, wherein will deliver to continuously in the electrolyzer of claim 24 by the antimony wash solution that method obtained of claim 28, antimony is by electrolytic extraction like this.

31. the method for a recovery is wherein carried out electrolytic extraction by the method for claim 29, and wherein by carrying out the dissolving again that electrolysis reduces antimony being lower than under 40 degrees centigrade the temperature.

32. the method for a selective recovery, wherein carry out electrolytic extraction by the method for claim 29, wherein use the secondary electrolyzer to come electrolytic extraction antimony, and wherein the bath voltage of the first step maintains 2.2 to 2.5 volts, and partial bath voltage maintain 1.8 to 2.0 volts.

33. the method for a selective recovery, wherein by in the first step electrolyzer of claim 30, add by claim 28 method produced have 20 or the wash solution of higher antimony/bi concns ratio come electrolytic extraction antimony, and wherein go out stream and add second stage electrolyzer the first step is electrolytic.

34. by the method for a kind of selective recovery of electrolytic extraction, wherein in the electrolyzer of the second stage, add by claim 28 method produced have 20 or the wash solution of lower antimony/bi concns ratio carry out electrolytic extraction.

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